Treatment of emulsions



Patented Feb. 6, 1951 TREATMENT vOF EMULSIONS L Fritz Fuchs fl olis'tongflexsassignor to Aqua nox Corporation; Houston, Teiciacorporation H of Texas No Drawing-3 Application April 27,1948, SeriakNo; 23,612

4 Claimszj (Ci. 252 358) 4 This application is a. continuation-impart. of my earlier. application, .Seri'alNo. '785,'549,' filed. November. :12, 1947.,1now Batent .no;,".2,4 2 ,473; granted December 27, 1949'.

This invention relates to the treatment of emulsions of mineral. oil ,and waten/such as petroleum emulsions, for the 1purpose ,,of fsepa.-.- rating the oil from the water.

An .object of this invention is to providea. novel process for breaking or separating petrp-.- leum emulsions by subjecting such emulsions to the action oil a novels-demulsifying composition to be described. in greater-"detail. hereinafter.

Anotherlobject isatheprovision -of, a novel demulsifier which is highly effective forwbreaking or separating, petroleum emulsions. w

The. demulsifier. described in the. aforementioned applicationcomprised. a. physical mixture. composed. of a water soluble. mahogany-,soap derived from petroleum, an oxidized fatty body, 20 and a compound ,comprising 3,3 polyoxyalkylene derivative. .of a hexahydric bodynwhich hassbeen.. partially esterified with-along-chain-fatty acid. I haveanow determined that highly efficient de-f mulsifying compositions may also.be providedby 25 employing a mixture -which includes both; the; mahogany soaps...derived from petroleum and the green acid soapslikewise.derived from petroleum along with the, other. components mentionedin the earlier application. .In still anothenmodifica 3n tion, the. water,-soluble. mahogany soaps a may be replaced entirely by the green-acidsoaps I This invention, therefore, .is directed to a demulsifying compositionwhich is a modification A of that. disclosed in the aforementioned application and comprises a physical mixture: composed of petroleum SuIfonates WhichE, may be either green acidsulfonates alone or both the-water soluble mahogany and greenacid,v sulphonate soaps derived from petroleum,.an oxidized 'fatty body,,and a compound comprising. a. po1yoxy.--=-. alkylene derivative of ahexahydric body-which hasb een partially esterified with a long-chain fatty. a cid;.

Thejwater-soluble,mahoganyv soapsare-WeH- known, commercia1ly available, materials which; s are derived from -petroleum distillates during conventional treatment. thereof by sulfuricacid the soaps beingmost often prepared in theform of ammonium, sodium' or potassium salts of them mahogany acids, Appropriate methods for the preparation'cr water-soluble mahogany soaps of. the lgind contemplatedherein are described in detail in U, S. Patents No. 2,317,050 to Goodloe e a1: a d,.. i9-i2l ,.i7.8 Ji B r er. g t ln th composition inaccordance with'this invention,"- the mahogany soapsemployed are thoseranging in molecular weight from about 250-500 and; 5 preferably those. of about e25 molecular weight: The'sodiumsoaps, particularly; of these acids are viscousiluids, reddish-amber'to brown in color and readily miscible with the othercomponents of the demulsifying composition contemplated by thiseinventionh V The greenacid sulphonate soaps are likewise thosecommonly obtained from the sulfuricacid; treatment. of petroleum distillates. and. are .'recovered from theacid layer and, prepared .g'enerallyfinv the formof the ammonium, sodium 'or potassium salts. vIn the composition. in accordance.

with this invention, theigreen sulphonic acids em-. ployed are those ranging in moleculanweight fromabout .250-450..and. preferably thoseabout .t 300-350 molecularv .weight. The ammoniumsoaps, particularly, of theseacids, in the form mostgenerally used, are viscous fluids practically black in color and readily miscible with the other components of the demulsifying.composi-. tion contemplated .by this invention.

The. oxidized fatty bodies employedmaywbe characterized. as the oxidized derivatives of the unsaturated fatty .oils or acids These include the various blown oils (or their fatty acids), such as blown castor, rapeseed,.soya, sesame, fish oils, 0leins,,.and many otherswderived from vegetable, animalor marine sources. The blown or oxidized fatty oils or fatty acids may be used singly'or mixtures of two -or more of them may be successu11yemployedin the composition in accordance with this invention. Cost will normally be the determining factor in the selection of the particular oxidized material which is employed. r The third principal component of the new coma position maybe characterized as a polyoxyalkylene derivativeof a hexahydric body which has beenpartially esterified-with a long-chainfatty acid. More specifically these materials are derived from the various hexahydric alcohols, such as mannitol,--sorbitol, and dulcitol, and their anhydrides, which include the sorbitans, sorbides, mannitans and mannides.- These hexahydric alcohol or anhydrides are partially'esterified with r long-chain fatty acids, such as oleic, palmitic, stearic, lauric, abietic,.and naphthenic acids to provide partial esters having several free hy, droxyl groups on the polyhydric body.. These. free hydroxyls are then further modified" by reaction with alkyleneoxide to produce av final compound havingboth freehydroxyl. and ether. cx nzssbstituentsswh ch provi e the;compound1;;

with desirable surface active, hydrophilic characteristics. These materials are commercially available under the trade name of Tweens and their physical and chemical characteristics are described in a pamphlet, entitled Atlas Spans and Atlas Tweens, reissued June 1945 by the Atlas Powder Company of Wilmington, Delaware.

In addition to the afore-described principal components of the composition in accordance with this invention, a quantity of a suitable thinning agent is usually added. These agents include such materials as ethyl alcohol, isopropyl alcohol, petroleum naphtha, solvent naphthas derived from coal and wood tar and other similar inert hydrocarbon solvents conventionally used for thinning demulsifying compounds.

Also, the final product may include a suitable agent for neutralizing or saponifying any free acids in the principal composition. Such agents may include the alkali hydroxides, ammonia, or the various basic amines, some examples of which are the mono-, di-, and tri-ethanolamines and their equivalents.

Following are several examples of the method of manufacturing compositions in accordance with this invention.

Example 1 200 pounds of water-soluble mahogany acids of about 425 molecular weight, in the form of the sodium salt, and 140 pounds of green petroleum sulfonic acids of about 300-350 molecular weigh in the form of their ammonium salts, are run into a steam jacketed kettle, equipped with a stirrer and thoroughly mixed, being heated to a temperature of about 140-150" F. The temperature employed is only such as is necessar to thin the materials sufficiently to permit easy stirring and thorough mixing of the ingredients, as no chemical reaction between the mixed materials is sought or is necessary. 60 pounds of commercial pale blown castor oil is then added to the kettle mixture and stirred therewith until a homogeneous mixture is obtained. Then 60 pounds of Tween 80 is added to the kettle mixture and stirred therewith until it is also completel dissolved. Tween 80 is the commercial name for the polyoxyalkylene derivative of sorbitan monooleate. The resulting composition is a clear dark brown-to-black colored viscous liquid and constitutes the primary demulsifying composition in accordance with this invention. To thin the mixture to a consistency suitable for eas han dling and application to oil field-emulsions, a quantity of an inert hydrocarbon thinner is mixed with the kettle product to dilute it to the desired consistency. In this example, the kettle product was thinned with 250 pounds of a mixture of two or more of the several inert thinners referred to above, to produce the final composition for use in treating petroleum emulsions.

Example 2 To the composition in accordance with Example 1, sufiicient strong ammonia (27 B.) was added to neutralize any free acidity in the composition. In the case of the Example 1 material, about 2% by weight of the ammonia was sufiicient for this purpose. The ammonia is preferably added to the kettle mixture of petroleum sulfonates and blown oil before the addition of the Tween 80 and the thinner. After suitable stirring to complete the neutralization reaction, the Tween 80 is added and thoroughly mixed with the neutralized material. following which, a

suitable quantity of thinner is added to produce the final demulsifier composition.

Exclusiv of the thinner, a typical composition will contain about -97% of a mixture of the petroleum sulfonates and blown fatty bodies, the relative proportions of these two classes of materials varying from 10-90% of either one or the other, as desired. As indicated previously the relative proportions of the green acid to mahogany sulfonates may vary from 0100% of each, that is, the petroleum sulfonate employed may be water-soluble mahogany soap, 100% green acid soap or any mixture thereof. The quantity of Tween 80 type material will range from 3 to 15% in the mixture of primary ingredients. This mixture of primary ingredients may be thinned by from about 10-50% of one of the classes of thinners mentioned, depending primarily upon the natur of the emulsion to be treated and the treating conditions employed.

A typical final composition in accordance with Example 1 above will contain the several ingredients in approximately the following weight proportions:

A typical composition of the Example 2 type will contain the same ingredients, modified as to proportions to include about 2% by weight of 27 B. ammonia.

In practicing the process, a treating agent or demulsifying agent of the kind above described may be brought in contact with the emulsion to be treated in an of the numerous ways now employed in the treatment of petroleum emulsions with chemical demulsifying agents, such, for example, as b introducing the treating agent into the well in which the emulsion is produced, introducing the treating agent into a conduit through which the emulsion is flowing, introducing the treating agent into a tank in which the emulsion is stored, or introducing the treating agent into a container that holds a sludge obtained from the bottom of an oil storage tank. In some instances, it may be advisable to introduce the treating agent into a producing well in such a way that it will become mixed with water and oil that are emerging from the surrounding strata, before said water and oil enter the .barrel of the well pump or the tubing up through which said water and oil flow to the surface of the ground. After treatment the emulsion is allowed to stand in a quiescent state, usually in a settling tank, at a temperature varying from atmospheric temperature to about 200 F., so as to permit the water or brine to separate from the oil, it being preferable to keep the temperature low enough so as to prevent the valuable constituents of the oil from Volatilizing. If desired, the treated emulsion may be acted upon by one or the other of various kinds of apparatus now used in the operation of breaking petroleum emulsions, such as homogenizers, hay tanks, gun barrels, filters, centrifuges, or electrical dehydrators.

The amount of treating agent on the anhydrous basis that is required to break the emulsion may vary from approximately 1 part of treating agent to 500 parts of emulsion, up to a ratio of 1 part of treating agent to 2 parts Oi em l ian, sispending upon the type or kind of emulsion being treated. In treating exceptionally refractory emulsions of the kind commonly referred to as tank bottoms or residual pit oils, the minimum ratio above referred to is often necessary, but in treating fresh emulsions, i. e., emulsions that will yield readily to the action of chemical demulsifying agents, the maximum ratio above mentioned will frequently produce highly satisfactory results. For the average petroleum emulsion of the water-in-oil type a ratio of 1 part of treating agent to 10,000 parts of emulsion will usually be found to produce commercially satisfactory results.

What I claim and desire to secure by Letters Patent is:

1. A demulsifier composition for breaking water-in-oil petroleum emulsions consisting essentially of 15 to 3% of a polyoxyalkylene derivative of a hexitol anhydride partially esterified with a long chain fatty acid, and 85 to 97% of a mixture of water-soluble mahogany and green acid soaps and an oxidized fatty body, the proportions of said soaps to said oxidized fatty body in said mixture ranging from of the one to 90% of the other, and the proportion of said mahogany acid soap to said green acid soap being about 10:7.

2. A demulsifier composition for breaking water-in-oil petroleum emulsions consisting essen tially of to 3% of a polyoxyalkylene derivative of sorbitan mono-oleate, and 85 to 97% of a mixture of water soluble mahogany and green acid soaps and an oxidized fatty body, the proportion of said soaps to said oxidized fatty body in said mixture ranging from 10% of the one to 90% of the other, and the proportion of said mahogany soap to said green acid soap being about 10:7.

3. A demulsifier composition for breaking wa- 'ter-in-oil petroleum emulsion consisting essentially of 15 to 3% of a polyoxyalkylene derivative of sorbitan mono-oleate, to 97% of a mixture esterified with a lon chain fatty acid, and 85 to 97% of a mixture of Water soluble mahogany and green acid soaps and an oxidized fatty body, the proportions of said soaps to said oxidized fatty body in said mixture ranging from 10% 0f the one to of the other, and the proportion of said mahogany soap to said green acid soap being about 10:7

FRITZ E. FUCHS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,872,286 Heckel et a1 Aug. 16, 1932 1,882,444 Pierce et a1 Oct. 11, 1932 1,940,394 De Groote et a1 Dec. 19, 1933 1,984,633 De Groote et al. Dec. 18, 1934 2,209,445 de Mering July 30, 1940 2,317,050 Goodloe et al Apr. 20, 1943 2,354,993 Harlan Aug. 1, 1944 2,355,778 Berger et a1 Aug. 15, 1944 2,443,273 Salathiel June 15, 1948 

1. A DEMULSIFIER COMPOSITION FOR BREAKING WATER-IN-OIL PETROLEUM EMULSIONS CONSISTING ESSENTIALLY OF 15 TO 3% OF A POLYOXYALKYLENE DERIVATIVE OF A HEXITOL ANHYDRIDE PARTIALLY ESTERIFIED WITH A LONG CHAIN FATTY ACID, AND 85 TO 97% OF A MIXTURE OF WATER-SOLUBLE MAHOGANY AND GREEN ACID SOAPS AND AN OXIDIZED FATTY BODY, THE PROPORTIONS OF SAID SOAPS TO SAID OXIDIZED FATTY BODY IN SAID MIXTURE RANGING FROM 10% OF THE ONE TO 90% OF THE OTHER, AND THE PROPORTION OF SAID MAHOGANY ACID SOAP TO SAID GREEN ACID SOAP BEING ABOUT 10:7. 